Latitudinal distributions of trace gases in and above the boundary layer

Statistical analyses of global atmospheric concentrations provide evidence that C₂Cl₄, CHCl₃ and CH₃CCl₃ (methylchloroform) are more abundant in the tropical boundary layer than above it (α ? 0.09) by 27% (±27%), 21% (?21%, +12%) and 6.4% (±6%) respectively. The air samples on which these results are based were collected by cryogenic techniques during the June 1978 project GAMETAG flights and analyzed soon afterwards by gas chromatography (EC/GC and GC/FID), thus providing latitudinal concentrations of CO, CH₄, CCl₃F, CCl₂F₂, CH₃CCl₃ and light C₂-hydrocarbons, both in and above the boundary layer. In August 1980, after further development of analytical techniques, the stored air samples were re-analyzed to establish the latitudinal distributions of CH₃I, CHCl₃, C₂Cl₄, C₂F₃Cl₃ (F-113) and CHClF₂ (F-22) in and above the boundary layer. Stability studies, spanning a year, show that the concentrations of these gases do not change in the flasks.     

A method of hazard assessment of a gaseous substance with respect to formation of toxic photodecomposition products. Application to CCl4, CCl3F and CCl2F2

CCl₄, CCl₃F and CCl₂F₂ decompose in ambient air forming highly toxic carbonyl halides etc. when exposed to sources of intense uv-emission, e.g. welding arcs. The resulting health hazard is assessed using a mathematical model.     

The production and release to the atmosphere of CCl3F and CCl2F2 (chlorofluorocarbons CFC 11 and CFC 12)

In order to understand the present concentration distribution of CCl₃F and CCl₂F₂ in the atmosphere and their atmospheric lifetimes, accurate data on the global production and release of these materials are needed. This paper reports improvements in the understanding of certain production and use categories which increase the accuracy of the estimates of these releases. However, lack of recent production data from certain sources prevents the total world production, and hence release, estimates from reflecting similar accuracy.     

The use of CFC-12, CFC-11 and CH3CCl3 to trace terrestrial airborne pollutant transport by land–sea breezes

Time-series observations of the atmospheric concentrations of the halocarbons, trichlorofluorocarbon (CFC-11), dichlorofluorocarbon (CFC-12), 1,2-trichlorofluoroethane (CFC-113), methyl chloroform (CH₃CCl₃) and carbon tetrachloride (CCl₄) were conducted at a site in Lukang, in Central Taiwan between April and August 2004. Fluctuations in atmospheric concentrations of CFC-11, CFC-12 and CH₃CCl₃ were generally driven by diurnal land–sea breeze and anthropogenic activity in this area. Elevated levels of CFC-11, CFC-12, and CH₃CCl₃ frequently occurred when the air was stagnant and the prevailing seaward land breeze was dominant. Atmospheric concentrations of CFC-113 and CCl₄ were much less variable relative to CFC-11, CFC-12 and CH₃CCl₃ during the same period, indicating that emissions of these two species from anthropogenic activities were small. The time-series distributions of atmospheric levels of CFC-12, CFC-11, CH₃CCl₃ and CO were characterized as a diurnal cycle with an elevated level at night and a low level during the daytime for most of the observed periods. As CFC-12, CFC-11 and CH₃CCl₃ behave as traffic- and industry-derived airborne pollutants in the urban atmosphere, they provide as a useful tracer in the application for the study of terrestrial airborne pollutants transport across the coastal area driven by land–sea breezes in this area.     

Simulation of long-range transport of acidic pollutants in East Asia during the Yellow Sand event

The atmospheric chemical process was simulated using the Carbon Bond 4 (CB-4) model, the aqueous-phase chemistry in Regional Acid Deposition Model and the thermodynamic equilibrium relation of aerosols with the emission inventories of the Emission Database for Global Atmospheric Research, the database of China and South Korea and the Mesoscale Model version 2 (MM5) meteorological fields to examine the spatial distributions of the acidic pollutant concentrations in East Asia for the case of the long-lasting Yellow Sand event in April 1998. The present models simulate quite well the observed general trend and the diurnal variation of concentrations of gaseous pollutants, especially for O₃ concentration. However, the model underestimates SO₂ and NO_x concentration but overestimates O₃ concentration largely due to uncertainty in NO_x and VOC emissions. It is found that the simulated gaseous pollutants such as SO₂, NO_x, and NH₃ are not transported far away from the source regions but show significant diurnal variations of their concentrations. However, the daily variations of the concentrations are not significant due to invariant emission rates. On the other hand, concentrations of the transformed pollutants including SO₄²⁻, NH₄⁺, and NO₃⁻ are found to have significant daily variations but little diurnal variations. The model-estimated deposition indicates that dry deposition is largely contributed by gaseous pollutants while wet deposition of pollutants is mainly contributed by the transformed pollutants.     

The Contribution of Sulfate and Nitrate to Atmospheric Fine Particles During Winter Inversion Fogs in Cache Valley,Utah

Abstract

Air pollutants were collected in Logan, Cache County, UT, in February 1993 during two periods of atmospheric inversion accompanied by fog. The following atmospheric species were determined: (1) gaseous SO₂, NO₂ (semi-quantitatively),HNO3, NH3, and HF; (2) fine particulate SO₄ ⁼, NO₃ ^-, NH₄ ⁺, F–, H⁺, C, Si, S, K, Ca, Ti, Mn, Fe, Ni, Cu, Zn, Pb, Se, Br, and Sr, and; (3) fine particulate mass, which was calculated. The major components of fine particulate matter were carbonaceous material, ammonium nitrate, and ammonium sulfate, while the soil component was small. Calculated, fine particulate mass averaged 80 μg/m³ and reached concentrations as high as 120 μg/m³. SO₂/So_x and NO₂/NO_y mole ratios generally varied between 0.2 and 0.1 during inversions. These ratios also showed moderate but consistent diurnal patterns. The emission inventory for Cache County indicates sources of SO₂ and NO_x but not significant amounts of primary sulfate and nitrate. The observations reported here indicate there is significant conversion of SO₂ and NO_x in the presence of excess oxidants to sulfuric and nitric acid that are neutralized by excess ammonia.     

Emission factors of atmospheric and climatic pollutants from crop residues burning

Biomass burning is a common agricultural practice, because it allows elimination of postharvesting residues; nevertheless, it involves an inefficient combustion process that generates atmospheric pollutants emission, which has implications on health and climate change. This work focuses on the estimation of emission factors (EFs) of PM_2.5, PM₁₀, organic carbon (OC), elemental carbon (EC), carbon monoxide (CO), carbon dioxide (CO₂), and methane (CH₄) of residues from burning alfalfa, barley, beans, cotton, maize, rice, sorghum, and wheat in Mexico. Chemical characteristics of the residues were determined to establish their relationship with EFs, as well as with the modified combustion efficiency (MCE). Essays were carried out in an open combustion chamber with isokinetic sampling, following modified EPA 201-A method. EFs did not present statistical differences among different varieties of the same crop, but were statistically different among different crops, showing that generic values of EFs for all the agricultural residues can introduce significant uncertainties when used for climatic and atmospheric pollutant inventories. EFs of PM_2.5 ranged from 1.19 to 11.30 g kg^?1, and of PM₁₀ from 1.77 to 21.56 g kg^?1. EFs of EC correlated with lignin content, whereas EFs of OC correlated inversely with carbon content. EFs of EC and OC in PM_2.5 ranged from 0.15 to 0.41 g kg^?1 and from 0.33 to 5.29 g kg^?1, respectively, and in PM₁₀, from 0.17 to 0.43 g kg^?1 and from 0.54 to 11.06 g kg^?1. CO₂ represented the largest gaseous emissions volume with 1053.35–1850.82 g kg^?1, whereas the lowest was CH₄ with 1.61–5.59 g kg^?1. CO ranged from 28.85 to 155.71 g kg^?1, correlating inversely with carbon content and MCE. EFs were used to calculate emissions from eight agricultural residues burning in the country during 2016, to know the potential mitigation of climatic and atmospheric pollutants, provided this practice was banned.

Implications: The emission factors of particles, short-lived climatic pollutants, and atmospheric pollutants from the crop residues burning of eight agricultural wastes crops, determined in this study using a standardized method, provides better knowledge of the emissions of those species in Latin America and other developing countries, and can be used as inputs in air quality models and climatic studies. The EFs will allow the development of more accurate inventories of aerosols and gaseous pollutants, which will lead to the design of effective mitigation strategies and planning processes for sustainable agriculture.     

Analysis of 3-year observations of CFC-11, CFC-12 and CFC-113 from a semi-rural site in China

In-situ measurements of atmospheric chlorofluorocarbons (CFCs) can be used to the assess their global and regional emissions and to check for compliance with phase-out schedules under Montreal protocol and its amendments. The atmospheric mixing ratios of CFC-11 (CCl₃F), CFC-12 (CCl₂F₂) and CFC-113 (CCl₂F–CClF₂) have been measured by an automated in-situ GC-ECDs system at the regional Chinese Global Atmosphere Watch (GAW) station Shangdianzi (SDZ), from November 2006 to October 2009. The time series for these three principal CFCs showed large episodic events and background conditions occurred for approximately 30% (CFC-11), 52% (CFC-12) and 56% (CFC-113) of the measurements. The mean background mixing ratios for CFC-11, CFC-12 and CFC-113 were 244.8 ppt (parts per trillion, 10^?12, molar) 539.6 ppt and 76.8 ppt, respectively, for 2006–2009. The enhanced CFC mixing ratios compared to AGAGE sites such as Trinidad Head (THD), US and Mace Head (MHD), Ireland suggest regional influences even during background conditions at SDZ, which is much closer to highly-populated areas. Between 2006 and 2009 background CFCs exhibited downward trends at rates of ?2.0 ppt yr^?1 for CFC-11, ?2.5 ppt yr^?1 for CFC-12 and ?0.7 ppt yr^?1 for CFC-113. De-trended 3-year average background seasonal cycles displayed small fluctuations with peak-to-trough amplitudes of 1.0 ± 0.02 ppt (0.4%) for background CFC-11, 1.3 ± 2.1 ppt (0.3%) for CFC-12 and 0.2 ± 0.4 ppt (0.3%) for CFC-113. On the other hand, during pollution periods these CFCs showed much larger seasonal cycles of 11.2 ± 10.7 ppt (5%) for CFC-11, 7.5 ± 6.5 ppt (2%) for CFC-12 and 1.0 ± 1.2 ppt (1.2%) for CFC-113, with apparent winter minima and early summer maxima. This enhancement was attributed to prevailing wind directions from urban regions in summer and to enhanced anthropogenic sources during the warm season. In general, horizontal winds from northeast showed negative contribution to atmospheric CFCs loading, whereas South Western advection (urban sector: Beijing) had positive contributions.     

Ion chromatographic determination of anions in rainwater

High acidity rainwater has recently become an issue in environmental pollution because of its great influence on ecological systems with special reference to the human environment. To solve this problem, the chemical behaviors of various pollutants in the air, particularly in the wet atmosphere must be studied. Ion chromatography was used for rapid analysis of trace amounts of anions.As a result, it was found that a combination of 2mM Na₂CO₃ and 5mM NaOH as an eluent was suitable for the separation of various anions. The reproducibility of determination of anions in standard solutions was found to be satisfactory with a coefficient of variation (CV) of 2–4% for F^?, Br^?, NO^?₃, SO^2?₃, SO^2?₄, and PO^3?₄, but not for NO^?₂. The determination of NO^?₂ was accomplished by preparing an eluent having almost the same composition and cencentration as that of the standard and sample solutions. The precision of the method with rainwater samples was less than 10%, and was considered to be usable for data analysis.In addition, a considerable number of ions in rainwater samples could be determined by using 1–3 ml of the sample without pretreatment. It was found that ion chromatography was one of the best means to obtain information on the chemical behaviors of trace amounts of anions in rainwater.     

Spatial and seasonal variations of elemental and ion components in air particulate matters in three mega-cities in China

Beijing–Tianjin–Hebei region is one of the most important political, economic and cultural centers of China. The rapid development of economy in last decades has caused severe air pollution problems, which has resulted in considerable harm to local ecological environment and human health. In this study, total 671 air samples were collected from Beijing, Tianjin and Shijiazhuang (the capital city in Hebei province), one reference site and four background sites in four seasons. Particulate matters (PMs) with different sizes, elements and dissolvable ions in PMs were analyzed. Pollutant concentrations, characteristics and seasonal variations were discussed in order to describe the pollution status and the possible sources in this region. Enriched factors of K, Ca, Cr, Fe, Cu, Zn, As, Cd and Pb were all higher than 10. Concentrations of dissolvable ions were in the order of NO₃^–, SO₄^2–>NH₄⁺>Cl^–>Ca²⁺, K⁺, Na⁺>Mg²⁺, F^–. NO₃^–, SO₄^2–, NH₄⁺, Cl^– were the most important ion pollutants in the three cities which accounted for 90.3–92.3% of total 9 ion concentrations. Ion concentrations in the PMs were in the order of PM₁>PM_1–2.5>PM_2.5–10>PM₁₀>TSP. More than 50% of the dissolvable ions exist in PM1 and the percentage increases to 73.9–94.8% in PM_2.5. Human activities should be the main sources of the metallic pollutants, among which coal combustion was identified as the primary one.     

Degradation of carbon tetrachloride by iron metal: Complexation effects on the oxide surface

Dehalogenation of chlorinated aliphatic contaminants at the surface of zero-valent iron metal (Fe⁰) is mediated by the thin film of iron (hydr)oxides found on Fe⁰ under environmental conditions. To evaluate the role this oxide film plays in the reduction of chlorinated methanes, carbon tetrachloride (CCl₄) degradation by Fe⁰ was studied under the influence of various anions, ligands, and initial CCl₄ concentrations ([P]_o). Over the range of conditions examined in these batch experiments, the reaction kinetics could be characterized by surface-area-normalized rate constants that were pseudo-first order for CCl₄ disappearance (k_CCl4), and zero order for the appearance of dissolved Fe²⁺ (k_Fe²⁺). The rate of dechlorination exhibits saturation kinetics with respect to [P]_o, suggesting that CCl₄ is transformed at a limited number of reactive surface sites. Because oxidation of Fe⁰ by CCl₄ is the major corrosion reaction in these systems, k_Fe²⁺ also approaches a limiting value at high CCl₄ concentrations. The adsorption of borate strongly inhibited reduction of CCl₄, but a concomitant addition of chloride partially offset this effect by destabilizing the film. Redox active ligands (catechol and ascorbate), and those that are not redox active (EDTA and acetate), all decreased k_CCl4 (and k_Fe²⁺). Thus, it appears that the relatively strong complexation of these ligands at the oxide–electrolyte interface blocks the sites where weak interactions with the metal oxide lead to dehalogenation of chlorinated aliphatic compounds.     

Sources of submicron aerosol during fog-dominated wintertime at Kanpur

The main objective of this atmospheric study was to determine the major sources of PM₁ (particles having aerodynamic diameter <1.0 μm) within and near the city of Kanpur, in the Indo-Gangetic Plain. Day and night, 10 h long each, filter-based aerosol samples were collected for 4 months (November 2009 to February 2010) throughout the winter season. These samples were subjected to gravimetric and quantitative chemical analyses for determining water-soluble ions (NH₄ ⁺, F^?, Cl^?, NO₃ ^?, and SO₄ ^2?) using an ion chromatograph and trace elements using an inductively coupled plasma–optical emission spectrometer. The mean PM₁ mass concentrations were recorded as 114?±?71 μg/m³ (day) and 143?±?86 μg/m³ (night), respectively. A significantly higher diurnal contribution of ions (NH₄ ⁺, F^?, Cl^?, NO₃ ^?, and SO₄ ^2?) in PM₁ mass was observed during the fog-affected days and nights throughout the winter season, for which the average values were recorded as 38.09?±?13.39 % (day) and 34.98?±?12.59 % (night), respectively, of the total PM₁ mass. This chemical dataset was then used in a source-receptor model, UNMIX, and the model results are described in detail. UNMIX provided a maximum number of five source factors, including crustal material, composite vehicle, secondary aerosol, coal combustion, and iron/steel production and metallurgical industries, as the dominant air pollution sources for this study.     

The continuous field measurements of soluble aerosol compositions at the Taipei Aerosol Supersite,Taiwan

The characteristics of ambient aerosols, affected by solar radiation, relative humidity, wind speed, wind direction, and gas–aerosol interaction, changed rapidly at different spatial and temporal scales. In Taipei Basin, dense traffic emissions and sufficient solar radiation for typical summer days favored the formation of secondary aerosols. In winter, the air quality in Taipei Basin was usually affected by the Asian continental outflows due to the long-range transport of pollutants carried by the winter monsoon. The conventional filter-based method needs a long time for collecting aerosols and analyzing compositions, which cannot provide high time-resolution data to investigate aerosol sources, atmospheric transformation processes, and health effects. In this work, the in situ ion chromatograph (IC) system was developed to provide 15-min time-resolution data of nine soluble inorganic species (Cl⁻, NO₂⁻, NO₃⁻, SO₄²⁻, Na⁺, NH₄⁺, K⁺, Mg²⁺ and Ca²⁺). Over 89% of all particles larger than approximately 0.056 μm were collected by the in situ IC system. The in situ IC system is estimated to have a limit of detection lower than 0.3 μg m⁻³ for the various ambient ionic components. Depending on the hourly measurements, the pollutant events with high aerosol concentrations in Taipei Basin were associated with the local traffic emission in rush hour, the accumulation of pollutants in the stagnant atmosphere, the emission of industrial pollutants from the nearby factories, the photochemical secondary aerosol formation, and the long-range transport of pollutants from Asian outflows.     

Daily Mortality and Air Pollution in the Netherlands

ABSTRACT

We studied the association of daily mortality with short-term variations in the ambient concentrations of major gaseous pollutants and PM in the Netherlands. The magnitude of the association in the four major urban areas was compared with that in the remainder of the country. Daily cause-specific mortality counts, air quality, temperature, relative humidity, and influenza data were obtained from 1986 to 1994. The relationship between daily mortality and air pollution was modeled using Poisson regression analysis. We adjusted for potential confounding due to long-term and seasonal trends, influenza epidemics, ambient temperature and relative humidity, day of the week, and holidays, using generalized additive models.

Influenza episodes were associated with increased mortality up to 3 weeks later. Daily mortality was significantly associated with the concentration of all air pollutants. An increase in the PM₁₀ concentration by 100 u.g/m³ was associated with a relative risk (RR) of 1.02 for total mortality. The largest RRs were found for pneumonia deaths. Ozone had the most consistent, independent association with mortality. Particulate air pollution (e.g., PM₁₀, black smoke [BS]) was not more consistently associated with mortality than were the gaseous pollutants SO₂ and NO₂. Aerosol SO₄ ^-2, NO₃ ^-, and BS were more consistently associated with total mortality than was PM₁₀. The RRs for all pollutants were substantially larger in the summer months than in the winter months. The RR of total mortality for PM₁₀ was 1.10 for the summer and 1.03 for the winter. There was no consistent difference between RRs in the four major urban areas and the more rural areas.     

Quality of roof runoff waters from an urban region (Gda sk, Poland)

The paper presents the results of testing of roof runoff waters from buildings in the city of Gda sk (Poland), carried out as a part of a broader research project aimed at the determination of pollutant levels in precipitation. The analytes determined included volatile organohalogen compounds, petroleum hydrocarbons, Na⁺, K⁺, NH₄⁺, Mg²⁺, Ca²⁺, F⁻, Cl⁻, NO₂⁻, NO₃⁻, PO₄³⁻, SO₄²⁻ ions, as well as organonitrogen, organophosphorus and organochlorine pesticides. In addition, the toxicity and pH of the samples were examined. The samples were collected over a period of six months, during or immediately following precipitation events. More than half of the samples (25) were found to be toxic, with inhibition exceeding 20%. The toxicity was weakly correlated to the levels of organonitrogen and organophosphorus pesticides in runoff waters. It was established that at least in some cases the roofing material affected the levels of the pollutants found in the samples.     

Distribution,Sources and Sinks of Atmospheric Halogenated Compounds

Based on two comprehensive field studies conducted in California, background concentration (parts per trillion) of N₂O (296.0 X 10³), SF₆ (0.16), CCI₂F₂ (180.8), CCI₃F (103.8), CCI₂FCCIF₂ (16.3), CCI₄ (114.2), CH₃CI (952.9), CHCI3 (23.4), CH₃I (2.4), CH3CCI3 (84.0), CCI₂CCI₂ (43.1), CHCICCI2 (14.5) and CH₃Br (—) have been reported. These trace constituents were identified using retention data on eight GC columns, their electron attachment properties, and their EC thermal response. All but CHCICCI₂ and CH₃Br were measurable 100% of the time at both sites. Cryogenic procedures for SF₆ ambient measurement were developed and successfully used. By an analysis of worldwide emissions of these trace constituents, their ambient levels, and their atmospheric lifetimes, it was possible to determine their origin (natural or anthropogenic). Our results indicate that 27% of organic chlorine contribution to the troposphere comes from fluorocarbons as opposed to a 73% contribution from the chloro-carbons. Further, the anthropogenic organic content in the troposphere was found to be about twice the natural content. Very high CHCI3 concentrations in onshore ocean waters were measured. Ambient data supporting the anthropogenic origin of CCI₄ have been presented.     

氯甲烷与偶氮染料混合废水的超声脱色

使用40 kHz超声(US)脱色氯甲烷(包括CCl4、CHCl3和CH2Cl2)与偶氮染料(包括甲基橙与铬黑T)混合模拟废水,考察了氯甲烷初始浓度对偶氮染料超声脱色和TOC去除的影响.结果表明:偶氮染料的单独超声脱色速率很慢;而在CCl4与CHCl3存在时超声能使偶氮染料短时间内脱色至无色,但对其TOC的超声去除促进作...     

Distribution Equilibrium of Mercury (II) Chloride between Water and Air Applied to Flue Gas Scrubbing

ABSTRACT

In the literature, different values of the distribution coefficient K_H for HgCl₂ between water and air are present in a range that spans more than 3 orders of magnitude. In order to determine if a waste incineration scrubber solution could become saturated with regard to HgCl₂, an accurate experimental determination of the distribution constant of HgCl₂ at elevated temperatures is needed. In this work, the coefficient has been determined at four different temperatures between 10 and 50 °C. The Arrhenius expression obtained is 5.5 x 10⁵ x exp[-(8060 ± 2200)/7] with a corresponding enthalpy for the process HgCl₂(aq)<» HgCl₂(g) of 67 ± 20 kJ/mole. K_H at 293 K was found to be ~5 x 10^-7 atm M^-1, which is in almost perfect agreement with an earlier study. Applying the obtained K_H values to waste incineration scrubber conditions shows that no major saturation effect will occur.     

Current and future emission estimates of exhaust gases and particles from shipping at the largest port in Korea

The emissions of exhaust gases (NO _x , SO₂, VOCs, and CO₂) and particles (e.g., PM) from ships traversing Busan Port in Korea were estimated over three different years (the years 2006, 2008, and 2009). This analysis was performed according to the ship operational modes (“at sea,” “maneuvering,” and “in port”) and ship types based on an activity-based method. The ship emissions for current (base year 2009) and future scenarios (years 2020 and 2050) were also compared. The annual emissions of SO₂, VOCs, PM, and CO₂ were highest (9.6?×?10³, 374, 1.2?×?10³, and 5.6?×?10⁵ ton year^?1, respectively) in 2008. In contrast, the annual NO _x emissions were highest (11.7?×?10³ ton year^?1) in 2006 due mainly to the high NO _x emission factor. The emissions of air pollutants for each ship operational mode differed considerably, with the largest emission observed in “in port” mode. In addition, the largest fraction (approximately 45–67 %) of the emissions of all air pollutants during the study period was emitted from container ships. The future ship emissions of most pollutants (except for SO₂ and PM) in 2020 and 2050 are estimated to be 1.4–1.8 and 4.7–6.1 times higher than those in 2009 (base year), respectively.